MXPA02002294A - Flameresistant polycarbonate blends. - Google Patents

Abstract

The invention relates to polycarbonate blends containing graft polymer, phosphanatamine and inorganic nanoparticles. The inventive polycarbonate blends have an improved flame resistance and improved mechanical properties, such as lowtemperature impact strength, elongation at break, weld line strength and resistance to stress cracking and an improved degree of yellowness.

Description

IGNIFUGE POLYCARBONATE MIXTURES FIELD OF THE INVENTION The present invention relates to polycarbonate / ABS blends, which contain phosphonatamines and inorganic nanoparticles, which have improved flame protection and improved mechanical properties such as low temperature notch resilience, good dilation breakage, strength of the joint seam and resistance to tearing under tension as well as an improved degree of yellowing. DESCRIPTION OF THE PRIOR ART US-PS 4 073 767 and 5 844 028 describe cyclic phosphorus compounds including phosphorylene rings as flame retardants suitable for polyurethanes, polycarbonates, polyesters, and polyamides. In US-P 4 397 750 certain cyclic phosphonate esters are described as effective flame retardants for polyols and for other polyolefins. US-P 5 276 066 and US-P 5 844 028 describe certain (1,3,2-dioxaphos-forinanmethane) -amines, which represent flame retardants suitable for polyurethanes, polyesters, polymers of styrene, PVC , PVAc or polycarbonate. US-P 3 505 431, FR-P 1 371 139, US -.P 3 711 577, US-P 4 054 544 describe acyclic trisphosphonatamines, which are partially halogenated. EP-A 0 640 655 describes molding compositions consisting of aromatic polycarbonate, styrene-containing copolymers and graft polymers, which can be finished in a flame-retardant manner with phosphorus compounds, monomers and / or oligomers. In EP-A-0 363 608 fireproof polymer mixtures consisting of aromatic polycarbonate, copolymer or graft copolymer as well as phosphates are described REF: 136165 oligomers as flame protection additive. For some applications, such as, for example, molding parts inside carcass parts, the thermal dimensional stability of these mixtures is often not sufficient. No. 5,061,745 describes polymer mixtures comprising aromatic polycarbonate, ABS graft polymer and / or styrene-containing copolymer and monophosphates as flame-protective additives. For the manufacture of parts for thin-walled housings, the level of resistance to tearing under tension of these mixtures is often insufficient. DETAILED DESCRIPTION OF THE INVENTION The task of the present invention consists in making available polycarbonate / ABS mixtures with high resistance to thermal deformation with improved flame resistance and with improved mechanical properties such as low temperature resilience, dilation to the breakage of the joint seam and resistance to tearing under tension as well as an improved degree of yellowing. This combination of properties is required, especially when they are used in the field of computer technology such as, for example, for monitor housings, printers or copiers. It has now been found that PC / ABS blends containing phosphonatamines in combination with inorganic nanoparticles have the desired properties. Thus the object of the invention are mixtures containing polycarbonate, and / or polyester carbonate, modifier of the resilience, phosphonatamines and inorganic powder with a mean particle diameter of less than 200 nm, which may contain other polymers, for example (co) thermoplastic vinyl polymers and / or polyalkylene terephthalates and, if appropriate, other additives. The polycarbonate blends contain, preferably from 0.1 to 30, in particular from 1 to 25, and very particularly preferably from 2 to 20 parts by weight of phosphonatamine of the formula (I) indicated below and, preferably from 0. , From 5 to 45, in particular from 1 to 25, and very particularly preferably from 2 to 15 parts by weight of the inorganic powder according to component E). The object of the invention are, preferably, mixtures containing A) from 40 to 99, preferably from 60 to 98.5 parts by weight of aromatic polycarbonate and / or polyester carbonate B) from 0.5 to 60, preferably from 1 to 40, in particular from 2 to 25. parts by weight of graft polymer of B.l) 5 to 95, preferably 30 to 80% by weight of one or more vinyl monomers on B.2) 95 to 5, preferably 20 to 70% by weight of one or more grafting bases with a glass transition temperature <10 ° C, preferably < 0 ° C, particularly preferably < -20 ° C, C) from 0 to 45, preferably from 0 to 30, particularly preferably from 2 to 25 parts by weight of at least one thermoplastic polymer selected from the group consisting of the vinyl (co) polymers and the polyalkylene terephthalates, D) of 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, particularly preferably 2 to 20 parts by weight of phosphonatamine of the formula (I) of phosphonatamine of the formula ( I) A3-yN-By (I), where A means a remainder of the formula (Ha) or (Ilb) R1 and R2 independently from each other, mean alkyl with 1 to 10 carbon atoms unsubstituted or substituted or signified aryl with 6 to 10 carbon atoms unsubstituted or substituted, R3 and R4 independently from each other, mean alkyl having 1 to 10 carbon atoms, unsubstituted or substituted or aryl with 6 to 10 carbon atoms unsubstituted or substituted or RJ and R4 together mean alkylene with 3 to 10 carbon atoms unsubstituted or substituted, and means the numerical values 0, 1 or 2 and B independently of each other, mean hydrogen, optionally halogenated alkyl with 2 to 8 carbon atoms, aryl with 6 to 10 carbon atoms unsubstituted or substituted, E) from 0.5 to 40, preferably from 1 to 25, particularly preferably from 2 to 15. parts by weight of finely divided inorganic powder, with an average particle diameter less than or equal to 200 nm. and F) from 0 to 5 parts by weight, preferably from 0.1 to 3 parts by weight, more preferably from 0.1 to 1 part by weight, very particularly preferably from 0.1 to 0.5 parts by weight by weight of a fluorinated polyolefin, giving 100 the sum of the parts by weight of all the components A + B + C + D + E + F. Component A. The aromatic polycarbonates and / or the aromatic polyester carbonates, suitable according to the invention, according to component A, are known from the literature or can be prepared according to processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, as well as DE -AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396, for the preparation of aromatic polyester carbonates, for example DE-OS 3 077 034). The preparation of the aromatic polycarbonates is carried out, for example, by reaction of diphenols with carbonyl halides, preferably phosgene and / or aromatic dicarbonyl dihalides, preferably benzene dicarbonyl dihalides, according to the limit surface process. where appropriate, using chain switches, for example monophenols and, if appropriate, using trifunctional branching agents or having a functionality greater than three, for example triphenols or tetraphenols. The diphenols for the preparation of the aromatic polycarbonates and / or the aromatic polyester carbonates are preferably those of the formula (II) (II), wherein A means a single bond, alkylene with 1 to 5 carbon atoms, alkylidene with 2 to 5 carbon atoms, cycloalkylidene with 5 to 6 carbon atoms, -O-, -SO-, -CO -, -S-, -SO2-, arylene with 6 to 12 carbon atoms, which may be condensed with other aromatic rings containing, if appropriate, heteroatoms, or a residue of the formulas (III) or (IV) B mean, respectively, alkyl having 1 to 12 carbon atoms, preferably methyl, halogen, preferably chlorine and / or bromine, x mean respectively independently of each other, 0, 1 or 2, p mean 1 or 0, and R5 and R6, which can be chosen individually for each X 1, independently, mean hydrogen or alkyl with 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, X 1 means carbon and m means an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one of the atoms X1, R5 and R6 simultaneously represent alkyl. Preferred diphenols are hydroquinone, resorcin, dihydroxydiphenols, bis- (hydroxyphenyl) -alkanes with 1 to 5 carbon atoms, bis- (hydroxyphenyl) -cycloalkanes with 5 to 6 carbon atoms, bis- (hydroxyphenyl) -ethers, bis- (hydroxyphenyl) -sulfoxy-two, bis- (hydroxyphenyl) -ketones, bis- (hydroxyphenyl) -sulfones and, a-bis- (hydroxyphenyl) -diisopropylbenzenes as well as their brominated derivatives in the nucleus and / or chlorinated in the core. Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis - (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl-sulfone and its di- and tetrabrominated or chlorinated derivatives, such as, for example, 2,2-bis (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) - propane. Particularly preferred is 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A). Individual diphenols or in the form of arbitrary mixtures can be used. Diphenols are known from the literature or can be prepared according to methods known from the literature. Chain switches suitable for the preparation of the aromatic, thermoplastic polycarbonates are, for example, phenol, p-chlorophenol, p-tert. -butylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 4- (1, 3-tetramethylbutyl) -phenol according to DE-OS 2 842 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert. -butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol. The amount of chain terminators used is, in general, between 0.5 mol% and 10 mol%, based on the sum in moles of the diphenols used in each case. The aromatic polycarbonates, thermoplastics, have weight average molecular weights (Mw, measured for example by ultracentrifuge or by measurement of the diffraction of light, from 10,000 to 200,000, preferably from 20,000 to 80,000.) The thermoplastic, aromatic polycarbonates can be branched from known, and specifically, preferably, by the incorporation of 0.05 to 2.0 mole%, based on the sum of the diphenols used, of trifunctional or trifunctional compounds or with a greater functionality than three, for example, those with three or more than three phenolic groups, Both homopolycarbonates and copolycarbonates are suitable.For the preparation of the copolycarbonates according to the invention according to component A, it is also possible to use 1 to 25% by weight, preferably from 2.5 to 25% by weight, (based on the total amount of diphenols used) of polydiorganosiloxanes with g hydroxy-aryloxy terminal groups. These are known (see, for example, US Pat. No. 3 419 634) or can be obtained according to methods known from the literature. The preparation of the copolycarbonates containing polydiorganosiloxane is described, for example, in DE-OS 3 334 782. Preferred polycarbonates are, in addition to the homopolycarbonates of bisphenol A, the copolycarbonates of bisphenol A with up to 15 mol%, based on the sum in moles of the diphenols, of other diphenols different from those which have been cited as preferred or as being especially preferred, especially 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane. The aromatic dicarbonyl dihalogenides for the preparation of the aromatic polycarbonate polyols are, preferably, the diacyl dichlorides of isophthalic acid, terephthalic acid, diphenylether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. . Mixtures of diacyl dichlorides of isophthalic acid and terephthalic acid in the ratio between 1: 20 and 20: 1 are particularly preferred. In obtaining polyester carbonates, it is used concomitantly, in addition, a carbonyl halide, preferably phosgene, as a bifunctional acid derivative. As chain terminators for the preparation of the aromatic polyester carbonates, in addition to the above-mentioned monophenols, also their esters of the chlorocarboxylic acids as well as the acyl chlorides of the aromatic monocarboxylic acids, which can be substituted, if appropriate , by alkyl groups with 1 to 22 carbon atoms or by halogen atoms, as well as the chlorides of the aliphatic monocarboxylic acids with 2 to 22 carbon atoms. The number of chain switches is respectively from 0.1 to 10% by mole, referred in the case of phenolic chain switches, to the moles of diphenols and, in the case of the chain-link chain monocarbonyl, to the moles of the dicarbonyl dichlorides. The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids. The aromatic polyester carbonates can be both linear and branched in a known manner (see also DE-OS 2 940 024 and DE-OS 3 007 934). Branching agents which may be used are, for example, trifunctional carbonyl chlorides or with a functionality greater than three, such as trimesin trichloride, cyanuric acid trichloride, 3,3'- 4,4'-benzophenone-tetrachloride. tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol%, (based on the dicarbonyl dichlorides used) or trivalent phenols or with a functionality greater than three, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4,4-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3-tri- (4-hydroxyphenyl) -benzene, 1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) - phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4-hydroxyphenyl) -methane, , 6-bis (2-hydroxy-5-methyl-benzyl) -4-methyl-phenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, tra- (4- [4-hydroxyphenyl-isopropyl] -phenoxy) -methane, 1,4-bis [4,4'-dihydroxytriphenyl) -methyl] -benzene, in amounts of 0.01 to 1.0 mol% , referred to the diphenols used. The phenolic branching agents can be arranged with the diphenols, the acyl chloride branching agents can be incorporated together with the acyl dichlorides. In the case of thermoplastic, aromatic polyester carbonates, the proportion of carbonate structural units can vary arbitrarily. Preferably, the proportion of carbonate groups is up to 100 mol%, especially up to 80 mol%, more preferably up to 50 mol%, based on the sum of the ester groups and the carbonate groups. Both the ester ratio and also the carbonate content of the aromatic polyester carbonates can be distributed in the polycondensate in block form or statistically. The relative solution viscosity (? Re?) Of the aromatic polycarbonates and the polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.22 to 1.3 (measured in solutions of 0.5 g. of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C). The thermoplastic, aromatic polycarbonates and the polyester carbonates can be used alone or in arbitrary mixtures with each other. Component B. Component B comprises one or more B-graft polymers of 5 to 95, preferably 30 to 80% by weight, of at least one vinyl monomer on B.2 of 95 to 5, preferably 70 to 20% by weight of one or more diene rubbers, in the form of particles with glass transition temperatures <10 ° C, preferably < 0 ° C, particularly preferably < -20 ° C. The graft base B.2 has, in general, an average particle size (value d50) from 0.05 to 5 μm, preferably from 0.10 to 0.5 μm, particularly preferably from 0.20 to 0.40 μm. The monomers B.sub.1 are preferably mixtures of Bl.l of 50 to 99 parts by weight of vinyllacromatoses and / or vinylaromatos substituted in the nucleus (such as, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or alkyl methacrylates (with 1 to 8 carbon atoms) (such as, for example, methyl methacrylate, ethyl methacrylate) and Bl .2 from 1 to 50 parts by weight of cyanide (vinyls) unsaturated such as acrylonitrile and methacrylonitrile) and / or (meth) acrylates of alkyl (with 1 to 8 carbon atoms) (such as, for example, methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic acid anhydride and N-phenyl-meleinimide). Preferred monomers Bl.l are chosen from at least one of the monomers formed by styrene, α-methylstyrene and methyl methacrylate, the preferred monomers Bl.sub.2 are selected from at least one of the monomers formed by acrylonitrile, acid anhydride. maleic and methacrylate methyl. The particularly preferred monomer B.sub.1 is styrene and B.sub.2 is acrylonitrile. The graft bases B.2, suitable for the graft polymers B, are, for example, diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and, if appropriate, diene, rubbers. of acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate. The preferred B.2 grafting bases are diene rubbers (for example based on butadiene, isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to Bl. and Bl .2), with the proviso that the vitreous transition temperature of component B.2 is below < 10 ° C, preferably < 0 ° C, particularly preferably < -10 ° C. Particularly preferred is pure polybutadiene rubber. Particularly preferred polymers B are, for example, ABS (emulsion, bulk and suspension ABS) polymers such as those described, for example, in DE-OS 2 035 390 (= US-PS 3 644 574) or in DE-OS 2 248 242 (= GB-PS 1 409 275) or in Ulmann, Enzyklopadie der Technischen Chemie, volume 19 (1980), page 280 et seq. The gel content of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene). The graft copolymers B are produced by radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization.

Particularly suitable grafting rubbers are also ABS polymers, which are produced by Redox initiation with an initiator system consisting of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285. Since, in the grafting reaction, they are not completely grafted As is known, the graft monomers on the graft base will be understood according to the invention by graft polymers B those products which are obtained by (co) polymerization of the graft polymers in the presence of the graft base and which are obtained concomitantly during processing. Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers formed by alkyl acrylates, optionally with up to 40% by weight, based on B.2 of other polymerizable ethylenically unsaturated monomers. Preferred polymerizable acrylic acid esters include alkyl esters with 1 to 8 carbon atoms, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halogen-alkyl esters with 1 to 8 carbon atoms, such as chloroethyl acrylate as well as mixtures of these monomers. For the crosslinking, monomers with more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers sorbers of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and monovalent unsaturated alcohols with 3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, such as for example ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as for example trivinyl cyanurate and triallyl; polyfunctional vinyl compounds, such as di- and tetravinylbenzenes; yes as well as triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds, which have at least 3 ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers formed by triallyl cyanurate, triallyl isocyanurate, triacryloylhexa-hydro-s-triazine, triallylbenzenes. The amount of the crosslinking monomers is preferably from 0.02 to 5, in particular from 0.05 to 2% by weight, based on the graft base B.2. In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups it is advantageous to limit the amount below 1% by weight of the base for graft B.2. The "other" preferred polymerizable monomers, ethylenically unsaturated, which can be used, in addition to the esters of acrylic acid, for the preparation of the base for grafting B.2, are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl alkyl ethers with 1 to 6 carbon atoms, methyl methacrylate, butadiene. Preferred acrylic rubbers as base for graft B.2 are emulsion polymers, which have a gel content of at least 60% by weight. Other suitable B.2 graft bases are silicone rubbers with active spots for grafting, such as those described in DE-OS 3 704 657, DE-OS 3 704 655. DE-OS 3 631 540 and DE- OS 3 631 539. The gel content of the B.2 graft bases is determined at 25 ° C in a suitable solvent (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag, Stuttgart 1977). The average particle size d50 is the diameter above and below which 50% by weight of the particles are respectively. This can be determined with the aid of ultracentrifugation measurement (W. Scholtan, H. Lange, Kolloid, Z, and Z. Polymere 250 (1972), 782-796) Component C. Component C covers one or more (co) polymers thermoplastic vinyl Cl and / or polyalkylene terephthalates C.2 .. As vinyl (co) polymers Cl are polymers of at least one monomer from the group consisting of vinylaromates, vinyl cyanides, (unsaturated nitriles), alkyl (meth) acrylates (with 1 to 8 carbon atoms), unsaturated carboxylic acids as well as derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. Especially suitable are (co) polymers consisting of Cl.l of from 50 to 99, preferably from 60 to 80, parts by weight of vinyllacromatoses and / or vinylaromatos substituted in the nucleus (such as, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or alkyl methacrylates (with 1 to 8 carbon atoms), (such as, for example, methyl methacrylate, ethyl methacrylate), and Cl. 2 from 1 to 50, preferably 20 up to 40 parts by weight of vinyl cyanides (unsaturated nitriles), such as acrylonitrile and methacrylonitrile and / or (meth) acrylates of alkyl (with 1 to 8 carbon atoms), (such as, for example, methyl methacrylate, -butyl, t-butyl acrylate) and / or unsaturated carboxylic acids (such as maleic acid) and / or derivatives (such as anhydrides and midas) of unsaturated carboxylic acids (e.g. maleic acid anhydride and N-phenyl-maleimide) . The (co) polymers C.l are resinous, thermoplastic and rubber-free. Particularly preferably, the C.l.l. copolymer is styrene and C.l. 2 is acrylonitrile.

The (co) polymers according to C.l are known and can be prepared by radical polymerization, especially by emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have molecular weights Mw (weight average determined by light scattering or by sedimentation) comprised between 15,000 and 200,000. The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols as well as mixtures of these reaction products. Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the components of dicarboxylic acids, terephthalic acid residues and at least 80% by weight, preferably at least 90% by weight, based on the diol component, of ethylene glycol and / or butanediol-1,4 residues. Preferred polyalkylene terephthalates can contain, in addition to the terephthalic acid residues, up to 20% by mole, preferably up to 10% by mole, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 carbon atoms or of dicarboxylic acids aromatics having 4 to 12 carbon atoms, such as, for example, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexane-diacetic acid. Preferred polyalkylene terephthalates can contain, in addition to the ethylene glycol or butanediol-1,4 moieties, up to 20% by mole, preferably up to 10% by mole of other aliphatic diols with 3 to 12 carbon atoms or diols cycloaliphatics with 6 to 21 carbon atoms, eg traces of propanediol-1,3, 2-ethylpropanediol-1,3, neopentyl glycol, pentanediol-1,5, hexanediol-1,6, cyclohexanedimethanol -1.4, of 3-ethylpenta-nodiol-2,4, of 2-methylpentanediol-2,4, of 2,2,4-trimethylpentanediol-1,3, of 2-ethylhexanediol-1,3, of 2, 2-diethylpropanediol-1, 3, hexanediol-2,5, 1,4-di- (β-hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4- dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis- (4-β-hydroxyethoxy-phenyl) -propane and 2,2-bis- (4-hydroxypropoxyphenyl) -propane (DE- OS 2 407 674, 2 407 776, 2 715 932). The polyalkylene terephthalates can be branched by incorporating relatively small amounts of tri or tetravalent alcohols or tri or tetrabasic carboxylic acids, for example according to DE-OS 1 900 270 and US-PS 3 692 744. Preferred examples of branching agents are trimesinic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. Particularly preferred are polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or butanediol-1,4, and mixtures of these polyalkylene terephthalates. The mixtures of the polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight of polyethylene terephthalates and from 50 to 99% by weight, preferably from 70 to 99% by weight. % by weight of polybutylene terephthalates. The polyalkylene terephthalates, which are preferably used, have, in general, a limit viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (proportion in weight 1: 1) at 25 ° C in the Ubbelohde viscometer. The polyalkylene terephthalates can be prepared according to known methods (see for example Kunststoff-Handbuch, Volume VIII, page 695 et seq., Carl-Hanser-Verlag, München 1973). Component D The molding compositions according to the invention contain, as flameproofing agents, at least one phosphonatamine compound of the formula (I) A3-y-N-By (I), in which A means where R1, R2, R3 and R4 as well as B e and have the meaning indicated above. Preferably, B means, independently of one another, hydrogen, ethyl, n- or iso-propyl, which may be substituted by halogen, aryl with 6 to 10 carbon atoms unsubstituted or substituted by alkyl having 1 to 4 carbon atoms and / or by halogen, especially phenyl or naphthyl. In R1, R2, R3 and R4, alkyl means, independently of each other, preferably methyl? ethyl, n-propyl, iso-propyl, n-, iso-, sec- or tere-butyl, pentyl or hexyl. In R.sub.1, R.sub.2, R.sub.3 and R.sub.4, substituted alkyl means, independently of one another, preferably, alkyl having 1 to 10 carbon atoms, substituted by halogen, especially means methyl, ethyl, n-propyl, iso-propyl, n-, iso -, sec- or tert-butyl, pentyl or hexyl substituted one or two times. R3 and R4, together with the carbon atom, with which they are linked, preferably form cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, especially cyclopentyl or cyclohexyl. In R.sup.1, R.sup.2, R.sup.3 and R.sup.4, aryl with 6 to 10 carbon atoms means independently, preferably, phenyl, naphthyl or binaphthyl, especially o-phenyl, o-naphthyl, o-binaphthyl, which may be substituted by halogen (generally one, two or three times). By way of example and by way of preference, the following are cited: 5,5,5 ', 5', 5", 5" -hexa-methyl-tris (1, 3,2-dioxaphosphorinanmetan) amin-2,2 ', 2"-trioxide the formula (1-1) (XPM 1000 Fa test product, Solutia Inc., St. Louis, USA) 1, 3,2-dioxaphosphorin-2-methanamine, N-butyl-N [(5, 5-dimethyl-1, 3,2-dioxaphosphorin -2-yl) methyl] -5,5-dimethyl-, P, 2-dioxide; l, 3,2-dioxaphosphorin-2-methanamine, N - [[5,5-dimethyl-1, 3,2-dioxaphosphorinan-2-yl) methyl] -5,5-dimethyl-N-phenyl-, P, 2-dioxide; 1, 3,2-dioxaphosphorinan-2-methanamine, N, N-dibutyl-5,5-dimethyl-, 2-oxide, 1,3,2-dioxaphos-forinan-2-methanimine, N - [(5, 5 -dimethyl-l, 3,2-dioxaphosphorinan-2-yl) methyl] -N-ethyl-5,5-dimethyl-, P, 2-dioxide, 1,2-dioxaphosphorinan-2-methanamine, N-butyl -N- [5,5-dichloro-methyl-l, 3,2-dioxaphosphorinan-2-yl) -methyl] -5,5-dichloromethyl-. P, 2-dioxide, 1,3,2-dioxa-phosphorinan-2-methanamine, N - [(5,5-di-chloromethyl-1, 3,2-dioxo-phospholin-2-yl) methyl] -5,5 -dichloromethyl-N-phenyl-, P, 2-dioxide; 1, 3,2-dioxaphosphorinan-2-methanamine, N, N-di- (4-chlorobutyl) -5,5-dimethyl-2-oxide; 1, 3,2-dioxaphosphorinan-2-methanimine, N - [(5,5-di-methyl-1, 3,2-dioxaphosphorinan-2-yl) methan] -N- (2-chloroethyl) -5,5 -di (chloromethyl) -, P2-dioxide. Also preferred are: Compounds of the formula (1-2) or (1-3) wherein R1, R2, R3 and R4 have the meanings indicated above. Particularly preferred are the compounds of the formula (1-2), (1-1). Also particularly preferred are the individual compounds mentioned above. The compounds of the formula (I) can be prepared according to the following procedure: a) PC13 is added to a mixture of 1, 3-diol derivatives, water and an organic solvent, at a temperature of 10-60 ° C. In this case, a 5,5-disubstituted 1,3,2-dioxaphosphorinan-2-oxide of the formula (la) is obtained wherein Ri and R2 have the meanings indicated above, b) after purification the l, 3,2-dioxaphosphorinan-2-oxide is reacted in paraformaldehyde, with an amine and NH 3 -y, where B and y have the meaning above indicated, c) after a further purification and drying, the phosphonatamine of the formula (I) is obtained. A detailed description of the obtaining process can be seen in the specification of the US patent 5 844 028. Component E. The component E comprises finely divided inorganic powders. The finely divided inorganic powders E, which are used according to the invention, are preferably constituted by at least one polar compound of one or more metals of the first to fifth major groups or of the first to eighth secondary groups of the Periodic Element System, preferably from the second to fifth major or fourth to eighth secondary groups, particularly preferably from the third to fifth major groups or fourth to eighth secondary groups with at least one element chosen from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon, Preferred compounds are, for example, oxides, hydroxides, hydrated oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, lithosides, hydrides, phosphites or IOSI itOS.

Preferably the finely divided powders are constituted by oxides, phosphates, hydroxides, preferably TiO2, SiO2, SnO2, ZnO, ZnS, boehmite, ZrO2, AI2O3, aluminum phosphates, in addition TiN, WC, AIO (OH), Sb2? 3, oxides of iron, NaSO, vanadium oxides, zinc borate, silicates, such as Al silicates, Mg silicates, mono-, di-, three-dimensional silicates. In the same way, mixtures or gifted compounds can be used.

In addition, these nonoescale particles can be modified superficially with organic molecules, to achieve a better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be generated. Especially preferred are aluminum oxides, for example boehmite or TiO2. The average diameters of the nanoparticles are less than or equal to 200 nm, preferably less than or equal to 150 nm, especially from 1 to 100 nm. The size of the particles and the diameter of the particles always means the average diameter d 50, determined with the help of ultracentrifuged measurements according to W. Scholtan et al., Kolloid-Z. And Z. Polymere 250 (1972), pages 782-796. The inorganic powder incorporates quantities of from 0.5 to 40, preferably from 1 to 25, particularly preferably from 2 to 15% by weight, based on the thermoplastic material, into the thermoplastic molding compositions. The inorganic compounds may be in the form of powders, pastes, sols, dispersions or suspensions. Powders can be obtained by precipitation from dispersions, sols or suspensions. The powders can be incorporated into the thermoplastic molding compositions by customary methods, for example by direct kneading or extrusion of the molding compositions and finely divided inorganic powders. The preferred processes are represented by the preparation of a masterbatch, for example in flame-retardant additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the coprecipitation of a thermoplastic component and the powders. finely divided inorganics, for example by coprecipitation of an aqueous emulsion and finely divided inorganic powders, if appropriate in the form of dispersions, suspensions, pastes or sols of finely divided inorganic materials Component F Fluorinated polyolefins F are of high molecular weight and have vitreous transition temperatures above -30 ° C, generally above 100 ° C, contained in fluorine, preferably from 65 to 76, especially from 70 to 76% by weight, average diameters of the particles d 0 from 0.05 to 1,000, preferably from 0.08 to 20 μm. In general, the fluorinated polyolefins F have a density of 1.2 to 2.3 g / cm3. Preferred fluorinated polyolefins F are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoro propylene copolymers and ethylene / tetrafluoroethylene copolymers. The fluorinated polyolefins are known (see "Vinyl and Related Polymers" by Schildknecht, John Wiley & amp;; Sons, Inc., New York, 1962, pages 484-494; "Fluorpolymers" by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Volume 13, 1970, pages 623-654; "Modern Plastics Encyclopedia", 1970-1971, volume 47, No. 10 A, October 1970, Me Graw-Hill, Inc., New York, pages 134 and 774; "Modern Plastic Encyclopedia", 1975-1976, October 1975, Volume 52, No. 10 A, Me Graw-Hill, Inc., New York, pages 27, 28 and 472 and US-PS 3 671 487, 3 723 373 and 3 838 092). These can be prepared according to known processes, for example by polymerization of tetrafluoroethylene in aqueous medium with a free radical-forming catalyst, for example sodium, potassium or ammonium peroxodisulfate, at pressures of 7 to 71 kg / cm2 and at temperatures of 0 to 200 ° C, preferably at temperatures of 20 to 100 ° C. (For more details see for example the US patent US 2 393 967). Depending on the application form, the density of these materials can be between 1.2 and 2.3 g / cm, the average particle size between 0.5 and 1,000 μm. The fluorinated polyolefins F, preferred according to the invention, are polymers of tetrafluoroethylene with an average particle diameter of 0.05 to 20 μm, preferably 0.08 to 10 μm, and a density of 1.2 to 1.9 g. / cm3 and are preferably used in the form of a coagulated mixture of emulsions of the polymers of tetrafluoroethylene F with emulsions of graft polymers B. Suitable fluorinated polyolefins F, which can be used in powder form, are polymers of tetrafluoroethylene with average particle diameter. from 100 to 1,000 μm and densities from 2.0 g / cm3 to 2.3 g / cm3. To obtain a coagulated mixture consisting of B and F, an aqueous emulsion (latex) of a graft polymer B is first mixed with a finely divided emulsion of a tetrafluoroethylene polymer F; Suitable emulsions of tetrafluoroethylene polymer usually have solids contents of from 30 to 70% by weight, in particular from 50 to 60% by weight, preferably from 30 to 35% by weight. The quantitative data in the description of component B may contain the part of the graft polymer for the coagulated mixture constituted by the graft polymer and by the fluorinated polyolefin. The equilibrium proportion in the emulsion mixture between the graft polymer B and the tetrafluoroethylene polymer F is from 95: 5 to 60:40. The emulsion mixture is then coagulated in a known manner, for example by spray drying, drying by lyophilization or coagulation by the addition of salts, acids, inorganic or organic bases, water miscible solvents, such as alcohols, ketones, preferably at temperatures from 20 to 150 ° C, especially from 50 to 100 ° C. If necessary, it can be dried at 50 to 200 ° C, preferably at 70 to 100 ° C. Suitable emulsions of tetrafluoroethylene polymer are commercially available and are offered, for example, by DuPont as Teflon ® 30 N. The molding compositions according to the invention can contain at least one of the usual additives, such as lubricants and mold release agents, nucleating agents, antistatics, stabilizers as well as dyes and pigments The molding compositions according to the invention can contain up to 35% by weight, based on the molding compound as a whole, of another flameproofing agent, given case of synergistic effect. For example, phosphorus compounds such as, for example, those described in EP-A 363 608, EP-A 345 522 and EP-A 640, will be cited as other flameproofing agents. 655, organic halogenated compounds such as decabromobisphenyl ether, tetrabromobisphenol, halogenated inorganic compounds, such as ammonium bromide, nitrogen compounds, such as melamine, melamine formaldehyde resins, inorganic hydroxy compounds such as Mg hydroxide, Al, inorganic compounds such as antimony oxides, barium metaborate, hydroxyantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate, talc, silicones, silicon dioxide and oxide of tin as well as siloxane compounds.

In addition, phosphorus compounds of the formula (V) are suitable as flameproofing agents, wherein R, R and R, independently of each other, mean an alkyl having 1 to 8 carbon atoms, optionally halogenated or a cycloalkyl having 5 or 6 carbon atoms, optionally halogenated and / or alkylated or an aryl with 6 to 30 carbon atoms, optionally halogenated and / or alkylated and / or aralkylated, and "n" and "1", independently of each other, mean 0 or 1. These phosphorus compounds are generally known (cf. for example, Ullmann, Enzyklopadie der technischen Chemie, volume 18, pages 301 et seq., 1979 and EP-A 345 522). Aralkylated phosphorus compounds have been described, for example, in DE-OS 38 24 356. Alkyl radicals with 1 to 8 carbon atoms, optionally halogenated, according to (V) can be halogenated one or more times, linear or branched.

Examples of alkyl radicals are chloroethyl, 2-chloropropyl, 2,3-dibromopropyl, butyl, methyl or octyl. Cycloalkyl with 5 or 6 carbon atoms, optionally halogenated and / or alkylated, according to (V) are cycloalkyls with 5 or 6 carbon atoms, if appropriate halogenated and / or alkylated one or more times, ie, for example, cyclopentyl, cyclohexyl, 3,3,5-trimethylcyclohexyl and fully chlorinated cyclohexyl.

The aryl radicals with 6 to 30 carbon atoms, optionally halogenated and / or alkylated and / or aralkylated, according to (V) have, if appropriate, one or more cores, are halogenated and / or alkylated and / or aralkylated. or several times, for example chlorophenyl, bromophenyl, pentachlorophenyl, pentabromophenyl, phenyl, cresyl, isopropylphenyl, phenyl and naphthyl substituted by benzyl. Preferably R, R and R stand for, independently of one another, methyl, ethyl, butyl, octyl, phenyl, cresyl, cumyl or naphthyl. Particularly preferably R, R and R stand for, independently of one another, methyl, ethyl, butyl, substituted phenyl, if appropriate, by methyl and / or ethyl. The phosphorus compounds which can be used according to the invention according to formula (V) are, for example, tributyl phosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromopropyl) phosphate, triphenyl phosphate. , tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) phosphate, tris- (p-benzylphenyl) phosphate, triphenylphosphine oxide, dimethyl metaphosphonate, diphenyl metaphosphonate and diethyl phenylphosphonate. Suitable flameproofing agents are also dimer phosphates and oligomers, such as those described, for example, in EP-A-0 363 608. The molding compositions according to the invention can contain protective agents. against the flame compounds of phosphorus according to formula (VI), In the formula R 10, R 11 R 12 and R 13 mean, independently of each other, respectively alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, aryl with 6 to 20 carbon atoms or aralkyl with 7 to 12 carbon atoms. carbon, optionally halogenated Preferably R10, R11, R12 and R13 mean, independently of each other, alkyl having 1 to 4 carbon atoms, phenyl, naphthyl or phenyl-alkyl having 1 to 4 carbon atoms. The aromatic groups R10, R11, R12 and R13 can be substituted, for their part, with halogen and / or alkyl groups, preferably with chlorine, bromine and / or alkyl with 1 to 4 carbon atoms. Especially preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl, and the corresponding brominated and chlorinated derivatives thereof. In the formula (VI) X means a mono or polynuclear aromatic radical with 6 to 30 carbon atoms. This is derived, preferably, from diphenols of the formula (I). Especially preferred are diphenol, bisphenol A, resorcinol or hydroquinone or their chlorinated or brominated derivatives. In formula (VI) n they can be, independently of each other, 0 or 1, preferably n is equal to 1. k means values from 0 to 30, preferably means an average value of from 0.3 to 20, particularly preferably from 0.5 to 10, especially from 0.5 to 6. Mixtures of 10 to 90% by weight, preferably 12 to 40% by weight, of at least one monophosphorous compound of the formula (V) and at least one phosphorus oligomer compound can also be used. or of a mixture of oligomeric phosphorus compounds such as those described in EP-A 363 608 as well as phosphorus compounds according to formula (VI) in amounts of 10 to 90% by weight, preferably 60 to 88% by weight, based on the total amount of the phosphorus compounds. The monophosphorus compounds of the formula (V) are, in particular, tributyl phosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-cresyl phosphate. , diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted arylphosphates, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl phenylphosphonate, triphenylphosphine oxide or tricresylphosphine oxide.

The mixtures consisting of the monomeric and oligomeric phosphorus compounds of the formula (VI) have on average k-values from 0.3 to 20, preferably from 0.5 to 10, especially from 0.5 to 6. The aforementioned phosphorus compounds are known (see, for example, the EP-A-363 608, EP-A-640 655) or can be prepared analogously according to known methods (for example Ullmanns Enzyklopadie der technischen Chemie, volume 18, pages 301 et seq., 1979; Houben-Weyl, Methoden der organischen Chemie, volume 12 / lm page 43; Beilstein volume 6, page 177). The molding compositions according to the invention, which contain the components A to F and, if appropriate, other known additives such as stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents, as well as antistatics, are prepared by mixing the corresponding components in known manner and by melt-kneading and melt extrusion at temperatures from 200 ° C to 300 ° C in conventional apparatuses such as internal kneaders, extruders and double-shaft spindles, the component E being preferably used in the form of the aforementioned coagulated mixture The mixing of the individual components can be carried out in a known manner both successively and simultaneously and, specifically, both at about 20 ° C (room temperature) and also at a higher temperature. The thermoplastic molding compositions according to the invention are suitable due to their excellent resistance to flame and resistance to thermal deformation as well as to their good properties such as strength of the joining seam and ESC behavior (tensile strength under tension ) for the manufacture of molded bodies of any kind, especially those with high demands on the resistance to breakage. The molding compositions of the present invention can be used for the production of moldings of any type. Especially molded bodies can be manufactured by injection molding. Examples of manufacturable molded bodies are: parts for housings of any kind, for example for household appliances such as juice squeezers, coffee machines, mixers, for office machines such as monitors, printers, copiers or cover plates for the sector of construction and parts for the automotive sector. They are also used in the field of electrical engineering, since they have very good electrical properties. Furthermore, the molding compositions according to the invention can be used for the production of the molded articles or of the following molded parts: parts for internal construction in railway vehicles, hubcaps, housings of electrical equipment, containing small transformers, housings for apparatus for the distribution and transmission of information, carcasses and coatings for medicinal purposes, massage devices and housings for the same, toy vehicles for children, flat wall elements, housings for safety devices, rear bumpers, thermal insulation, containers for transport, devices for the maintenance and care of small animals, parts molded for sanitary and bathroom equipment, cover grilles for ventilation holes, molded parts for garden sheds and tools and housings for gardening devices. Another form of transformation consists in the manufacture of molded bodies by drawing from plates or sheets previously manufactured. Another object of the present invention therefore consists in the use of the molding compositions according to the invention for the production of moldings of any type, preferably those mentioned above, as well as the moldings constituted by the moldings. molding compositions according to the invention. Examples Component A Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.252, measured in CH2Cl2 as solvent at 25 ° C and at a concentration of 0.5 g / 10 ml. Component B Graft polymer of 40 parts by weight of a copolymer formed by styrene and acrylonitrile in the proportion of 73:27 on 60 parts by weight of cross-linked polybutadiene rubber, in the form of particles (average diameter of the particles d50-0 , 28 μm), manufactured by emulsion polymerization. Component C Styrene / acrylonitrile copolymer with a weight ratio of styrene / acrylonitrile of 72:28 and with a limit viscosity of 0.55 dl / g (measured in dimethylformamide at 20 ° C). Component D Phosphonatamine of the formula: (XPM 1000 development product from Solutia Inc., St. Louis, USA). 5 C m-.component E Pural® 200, an aluminum oxide hydroxide (Fa. Condea, Hamburg, Germany), with average particle sizes of approximately 50 nm. Component F Tetrafluoroethylene polymer as a coagulated mixture constituted by a SAN-graft polymer emulsion according to component B above indicated in water and a tetrafluoroethylene polymer emulsion in water. The mixing ratio between graft polymer B and the tetrafluoroethylene polymer E in the mixture is 90% by weight relative to 10% by weight, the tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the mean diameter of the particles is between 0.05 and 0.5 μm. The SAN-graft polymer emulsion has a solids content of 34% by weight and an average diameter of the latex particles of ds0 = 0.28 μm. Obtaining F The emulsion of the tetrafluoroethylene polymer (Teflon 30 N of the firm DuPont) is mixed with the graft polymer emulsion of SAN B and stabilized with 1.8% by weight, based on the graft polymer, of phenolic antioxidants. The mixture is coagulated at 85 to 95 ° C with an aqueous solution of MgSO4 (bitter salt) and acetic acid at pH 4 to 5, filtered and washed until it is practically free of electrolytes, then it is released by centrifugation of the amount * -, - water and then dried at 100 ° C to give a powder. This powder can then be mixed with the other components in the described devices. Obtaining and testing the molding compositions according to the invention The mixing of the components is carried out in an internal 3-liter kneader. The molded bodies are manufactured in an injection casting machine of the Arburg 270 E type at 260 ° C. The determination of the dimensional stability to heat according to Vicat B is carried out in accordance with DIN 53 460 (ISO 306) in bars with dimensions of 80 x 10 x 4 mm. The determination of the notched resilience is carried out according to ISO 180/1 A. To determine the strength of the joint seam, it is measured according to DIN 53 453, on the joining seam of specimens cast by injection on both sides (processing temperature 260 ° C) with dimensions of 170 x 10 x 4 mm The combustion behavior of the samples is measured according to UL-Subj. 94 V in bars with dimensions of 127 x 12.7 x 1.6 mm, manufactured in an injection molding machine at 260 ° C. The UL 94 V test is carried out in the following manner: The samples of the substance are molded to give bars with dimensions of 127 x 12.7 x 1.6 mm. The jibs are mounted vertically so that the bottom side of the specimen is 305 mm above a strip of gauze. Each test strip is individually ignited by means of two successive ignition processes with a duration of 10 seconds, the combustion properties are observed after each ignition process and then the sample is evaluated. A Bunsen burner with a blue flame height of 100 mm (3.8 inches) of natural gas with a thermal unit of 3.73 x 104 kJ / m3 (1000 BTU per cubic foot) is used to ignite the displays.

The UL 94 V-O classification covers the properties described below of materials that are tested according to the UL 94 V standard. Molding compositions of this class do not contain samples that burn more than 10 seconds after the action of the test flame; they do not show total combustion times greater than 50 seconds in the case of a double action of the flame on each group of samples; they do not contain samples that burn completely up to the clamp, held at the upper end of the sample; they do not present samples that burn the gauze arranged below the sample due to droplets or particles in combustion; they also do not contain samples that are incandescent more than 30 seconds after the test flame is removed. Other UL 94 classifications designate samples that are less flame retardant or that are less self-extinguishing, since they produce droplets or particles in combustion. These classifications are designated UL 94 V-l and V-2. N.B. means "not approved" and is the classification of samples that show subsequent burn times of > 30 seconds. The tensile behavior under tension (ESC behavior) is tested on bars with dimensions of 80 x 10 x 4 mm, processing temperature 260 ° C. A mixture consisting of 60% by volume of toluene and 40% by volume of isopropanol is used as the test medium. The specimens are subjected to a pre-dilation by means of a template in the form of a circle arc (prior dilation in percentage) and stored at room temperature in the test medium. The tensile behavior under tension is evaluated by means of cracking or breaking according to the previous expansion and the test medium. In Table 1 below, a compilation of the properties of the molding compositions according to the invention has been given.

By using the combination formed by the phosphonatamine and the finely divided inorganic powder, molding compositions with a high resistance to thermal deformation are obtained, which are characterized by very good mechanical properties such as notch resilience at low temperatures, tearing under tension, resistance of the seam of union and expansion to the break as well as by a reduced degree of yellowing. The flame protection of the molding compositions according to the invention is clearly improved by the addition of the finely divided inorganic powder. Table: Molding masses and their properties N.B. = Not approved It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Claims (1)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1.- Mixtures characterized by containing polycarbonate and / or polyester carbonate graft polymer, phosphonatamine and inorganic powder with an average particle diameter less than or equal to 200. nm. 2. Mixtures according to claim 1, characterized in that they contain from 0.1 to 30 parts by weight of phosphonatamine of the formula (I) in which A means a radical of the formula (lia) or (Ilb) R1 and R2 independently from each other, mean alkyl with 1 to 10 carbon atoms unsubstituted or substituted or signified aryl with 6 to 10 carbon atoms unsubstituted or substituted, R3 and R4 independently from each other, mean alkyl having 1 to 10 carbon atoms, unsubstituted or substituted or aryl with 6 to 10 carbon atoms unsubstituted or substituted or R3 and R4 together mean alkylene with 3 to 10 carbon atoms unsubstituted or substituted, and means the numerical values 0, 1 or 2 and B independently of each other, mean hydrogen, optionally halogenated alkyl with 2 to 8 carbon atoms, aryl with 6 to 10 carbon atoms unsubstituted or substituted, and from 0.5 to 40 parts by weight of finely divided inorganic powder, the quantitative indications referring to the group of mix. 3. Mixtures according to claims 1 to 3, characterized in that they contain A) from 40 to 99 parts by weight of aromatic polycarbonate and / or polyestercarbonate B) from 0.5 to 60 parts by weight of graft polymer of B. 5 to 95% by weight of one or more vinyl monomers on B.2) 95 to 5% by weight of one or more graft bases with a vitreous transition temperature < 10 ° C, C) from 0 to 45 parts by weight of at least one thermoplastic polymer selected from the group consisting of the vinyl (co) polymers and polyalkylene terephthalates, D) from 0.1 to 30 parts by weight of a phosphonatamine of the general formula (I) according to claim 1, E) from 0.5 to 40 parts by weight of finely divided inorganic powder with an average particle diameter less than or equal to 200 nm, and F) from 0 to 5 parts by weight of fluorinated polyolefin, giving 100 the sum of the parts by weight of all the components of the mixture. 4. Mixtures according to claims 1 to 3, characterized in that they contain from 60 to 98.5 parts by weight of A, from 1 to 40 parts by weight of B, from 0 to 30 parts by weight of C, from 1 to 25. parts by weight of D, from 1 to 25 parts by weight of E, from 0, 15 to 1 part by weight of F. 5. Mixtures according to claims 1 to 4, characterized in that they contain from 2 to 25 parts by weight of C. 6. Mixtures according to claims 1 to 5, characterized in that they contain from 2 to 20 parts by weight of D. 7 '.- Mixtures according to the preceding claims, characterized in that the vinyl monomers B. 1 are mixtures consisting of B. l. from 50 to 99 parts by weight of vinyllacromatos and / or of vinylaromatos substituted in the nucleus and / or of methacrylates of alkyl (with 1 to 8 carbon atoms) and B.1.2 of 1 to 50 bread by weight of vinyl cyanides and / o of. (Meth) alkyl acrylates (with 1 to 8 carbon atoms) and / or unsaturated carboxylic acid derivatives. 8 - Mixtures according to the preceding claims, characterized in that the graft base is chosen from at least one rubber from the group consisting of diene rubbers, EP (D) M rubbers, acrylate rubbers, polyurethane rubbers, silicone rubbers, chloroprene and ethylene / vinyl acetate 9. - Mixtures according to the preceding claims, characterized in that the component D is selected from the group consisting of 5.5.5 5 ', 5", 5" -hexamethyltris (1, 3,2-dioxaphosphorinanmetan) amino-2,2', 2"-trioxide I, 3,2-dioxaphosphorin-2-methanamine, N-butyl-N [(5,5-dimethyl-1,3,2-dioxaphosphorin-2-yl) methyl] -5,5-dimethyl- , P, 2-dioxide; l, 3,2-dioxaphosphorin-2-methanamine, N - [[5,5-dimethyl-1, 3,2-dioxaphos-forinan-2-yl) methyl] -5,5-dimethyl-N-phenyl-, P, 2-dioxide; 1, 3,2-dioxaphosphorinan-2-methan-amine, N, N-dibutyl-5,5-dimethyl-, 2-oxide, 1, 3,2-dioxaphosphorinan-2-methanimine, N - [(5,5 -dimethyl-l, 3,2-dioxaphosphorinan-2-yl) methyl] -N-ethyl-5,5-dimethyl-, P, 2-dioxide, 1,3, 2-dioxaphosphorinan-2-methanamine, N-butyl-N - [5,5-dichloro-methyl-l, 3,2-dioxaphosfori-nan-2-yl) -methyl] -5,5-dichloromethyl-. P, 2-dioxide, 1, 3,2-dioxa-phosphorin-2-methanamine, N - [(5,5-di-chloromethyl-1, 3,2-dioxamphosphorin-2-yl) methyl] -5 , 5-dichloro-methyl-N-phenyl-, P, 2-dioxide; 1, 3,2-dioxaphosphorinan-2-methanamine, N, N-di- (4-chlorobutyl) -5,5-dimethyl-2-oxide; l, 3,2-dioxaphosphorinan-2-methanimine, N - [(5,5-di-methyl-l, 3,2-dioxa-phosphorinan-2-yl) methan] -N- (2-chloroethyl) -5 , 5-di (chloromethyl) -, P2-dioxide. 10. Mixtures according to the preceding claims, characterized in that the component E is chosen from at least one polar compound of one or more metals of the first to fifth major groups or first to eighth secondary elements of the Periodic Table of the Elements with at least one element chosen from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon. 11. Mixtures according to claim 10, characterized in that the component E is chosen from at least one polar compound of one or several metals of the second to fifth major groups or fourth to eighth secondary groups with at least one element chosen from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon. 12. Mixtures according to claim 11, characterized in that the component E is chosen from at least one polar compound of one or more metals of the third to fifth major or fourth to eighth secondary groups of the Periodic Table of the Elements with at least one element chosen from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon. 13. Mixtures according to the preceding claims, characterized in that the component E is chosen from at least one oxide, hydroxide, hydrous oxide, sulfate, sulfite, sulfide, carbonate, carbide, nitrate, nitrite, nitride, borate, silicate, phosphate hydride, phosphite and phosphonate. 14. Mixtures according to one of the preceding claims, characterized in that the component E is chosen from oxides, phosphates and hydroxides. 15. Mixtures according to one of the preceding claims, characterized in that the component E is chosen from TiO2, SiO2, Sn? 2, ZnO, ZnS, boehmite, ZrO2, AI2O3, aluminum phosphates, iron oxides, TiN, WC, AIO (OH), Sb2? 3, Na2S? 4, vanadium oxides, zinc borate, silicates, such as Al silicates, Mg silicates, mono-, di-, three-dimensional silicates, their mixtures or compounds. 16. Mixtures according to the preceding claims, characterized in that the component E is chosen from the hydrated aluminum oxides, TiO2 and mixtures thereof 17. Mixtures according to the preceding claims, characterized in that they contain at least one additive, chosen from the group formed by lubricants and mold release agents, nucleating agents, antistatics, stabilizers, dyes and pigments. 18. Mixtures according to the preceding claims, characterized in that they contain other flameproofing agents, which are different from the components D. 19. Process for obtaining molding compositions according to claims 1 to 18, characterized in that the components A to F and, if necessary, other additives, and melt-kneading. 20. Use of the molding compositions according to claims 1 to 18 for the production of molded cores. 21.- Molded shapes characterized in that they are obtained from the molding compositions according to one of claims 1 to 18. 22. Parts for housing according to claim 21.